CN106807335A - Magnetic retention polyamino adsorbent particulate material, preparation method and applications - Google Patents

Magnetic retention polyamino adsorbent particulate material, preparation method and applications Download PDF

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Publication number
CN106807335A
CN106807335A CN201510882775.0A CN201510882775A CN106807335A CN 106807335 A CN106807335 A CN 106807335A CN 201510882775 A CN201510882775 A CN 201510882775A CN 106807335 A CN106807335 A CN 106807335A
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polyamino
magnetic
heavy metal
adsorbent
magnetic retention
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范力仁
周洋
范羽仪
郑曼洁
宋吉青
张引
周小丹
刘路
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China Ground Golden Shield Environment Technology Co ltd
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China Ground Golden Shield Environment Technology Co ltd
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Priority to CN201510882775.0A priority Critical patent/CN106807335A/en
Priority to PCT/CN2015/097527 priority patent/WO2017088216A1/en
Publication of CN106807335A publication Critical patent/CN106807335A/en
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    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
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    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
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    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
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    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
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    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28002—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their physical properties
    • B01J20/28009—Magnetic properties
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    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
    • B01J20/28016—Particle form
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/28—Treatment of water, waste water, or sewage by sorption
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    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • C02F1/288—Treatment of water, waste water, or sewage by sorption using composite sorbents, e.g. coated, impregnated, multi-layered
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    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F11/00—Treatment of sludge; Devices therefor
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F11/00—Treatment of sludge; Devices therefor
    • C02F11/004—Sludge detoxification
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    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2220/00—Aspects relating to sorbent materials
    • B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
    • B01J2220/46—Materials comprising a mixture of inorganic and organic materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2220/00—Aspects relating to sorbent materials
    • B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
    • B01J2220/48—Sorbents characterised by the starting material used for their preparation
    • B01J2220/4806—Sorbents characterised by the starting material used for their preparation the starting material being of inorganic character
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B01J2220/00—Aspects relating to sorbent materials
    • B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
    • B01J2220/48—Sorbents characterised by the starting material used for their preparation
    • B01J2220/4812—Sorbents characterised by the starting material used for their preparation the starting material being of organic character
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B01J2220/00—Aspects relating to sorbent materials
    • B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
    • B01J2220/48—Sorbents characterised by the starting material used for their preparation
    • B01J2220/4812—Sorbents characterised by the starting material used for their preparation the starting material being of organic character
    • B01J2220/4825—Polysaccharides or cellulose materials, e.g. starch, chitin, sawdust, wood, straw, cotton
    • C—CHEMISTRY; METALLURGY
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  • Environmental & Geological Engineering (AREA)
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Abstract

The present invention relates to the magnetic retention polyamino adsorbent particulate material of many amine groups of Surface coating, particle size range is 0.5-500.0 μm, with inorganic organic many shell core-shell structures and carbonnitrogen bond connection polyamino adsorption group rock-steady structure.Preparation method mainly includes following basic step：1. inorganic matter clad is prepared：2. surface double-bond：3. Coated with Organic Matter layer is prepared：4. magnetic retention polyamino adsorbent particulate material is prepared.The magnetic retention polyamino adsorbent particulate material can in wide ph range with water body, solid-liquid suspension（Mixing）In system there is selective chemical suction-operated in heavy metal substance, while having easily by magnet or concentration equipment from water body, solid-liquid suspension（Mixing）Separated in system, the advantage that the renewable reuse of material, heavy metal can be centrally disposed, the industries such as environmental protection, pollution control, heavy metal substance recovery, ore dressing, hydrometallurgy can be widely used in.

Description

Magnetic retention polyamino adsorbent particulate material, preparation method and applications
Technical field
The present invention relates to magnetic retention polyamino adsorbent particulate material, preparation method and applications, belong to new material and money Source environmental area.
Background technology
Current heavy metal pollution problem of administering has turned into a whole world environmental problem urgently to be resolved hurrily.Wherein water pollution is main Refer to water body（Including river, lake, reservoir, ocean and industrial water, discharge water and Drinking Water etc.）Suffer heavy metal classes The pollution of pollutant, including cadmium, lead, mercury, chromium, arsenic etc., pollution source is mainly industrial wastewater, such as ore dressing plant, Electroplate Factory, steel The waste water of the discharges such as factory.
In addition to the heavy metal that itself contains, remaining is then because pollution makes heavy metal enter soil to heavy metal in soil In.Heavy metal pollution of soil is essentially from 3 each side：The sedimentation of heavy metal in air, for example, the waste gas of industrial production discharge, Leaded vehicle exhaust etc. passes through natural subsidence and drenches with rain to settle into soil；Irrigated using the sewage containing heavy metal, caused The increase of soil weight Cd, As, Cu equal size；In addition, the plastic film of daily life, the fertilizer and pesticide of agricultural application also cause Soil pollution.
Current heavy metal method for governing pollution mainly has four classes, except conventional chemical methods, Physical, biological harnessing method Outward, it is that a class is sent out using " the environmentally conscious materialses method " of special construction and property the improvement heavy metal pollution of soil of environmentally conscious materialses The methods for curing heavy metal contamination in soil of exhibition, has shown advantage.Particularly novel magnetic solid chelant granular materials technology, Heavy metal substance that can not only be in selective absorption heterogeneous system, but also material magnetic property in itself can be utilized, use magnetic Iron separates it with heterogeneous system, reaches the purpose for removing heavy metal.
Similar to soil heterogeneous system, other, such as deposited extensively in trade waste, agriculture wastes, cities and towns discarded object Heavy metal pollution need remove problem, meanwhile, also have in other resource and environment materials plurality of heavy metal, valuable metal, Noble metal is needed to be extracted using novel magnetic solid chelant material, recycled.
Applicant has applied for multinomial patent of invention in terms of novel magnetic solid chelant material technology. In CN201210045129 patents of invention, there is provided a kind of magnetic expansion adsorption composite material and preparation method thereof.The composite wood Material by magnetic powder, non-metallic mineral powder, water-soluble vinyl unsaturated monomer and crosslinking agent by polymerisation it is compound and Into with network structure, heavy metal material has the advantages that adsorption capacity is big, manufacture method is simple, low cost. In CN201410080511 patents of invention, there is provided a kind of magnetic ammonia carboxylic chelating adsorption particle material and preparation method thereof, it with The SiO of internal coated magnetic material2Particle as core shell structure, by surface modification in shell SiO2Upper introducing amino, then in ammonia Obtained from carrying out carboxy methylation on base.In application for a patent for invention 200510062264.4, there is provided adsorb base containing organic sulfur The magnetic retention organic sulfur adsorbent particulate material of group, organic sulfur adsorption group can be sulfydryl, sulfide group, dithiocarbamic acid group Deng.In application for a patent for invention 201510010306.X, there is provided a kind of magnetic separation isolation of purified for removing heavy metal pollution of soil Processing tecchnics, it is characterised in that it is carried out absorption and caught with reactivity or adsorptivity magnetic carrier particles material to the heavy metal in soil Collection, then carries out magnetic separation and is separated with soil, includes successively：1. soil prepares and the step of mud processed；2. magnetic carrier adsorbing and trapping The step of heavy metal；3. the step of magnetic separation is separated；4. the step of material regeneration；5. the step of recovery heavy metal is centrally disposed.Should Invention can make up existing heavy metal pollution of soil, chemical method, Physical, bioanalysis and carry out the deficiency of soil remediation presence, with method letter Single, magnetic carrier particles material can be low with recycling utilization, treatment cost, can play the excellent of technique of preparing and benficiation machinery Gesture, can carry out large, medium and small various scale Heavy Metals in Soil Contaminated and remove decrement purification reparation, and overall process is without a large amount of dirts（It is useless）Aquatic products It is raw, do not cause secondary pollution or strange land to pollute, and heavy metal can be reclaimed.
In addition, Hu Jianbang etc. exists《Using chemical industry》Paper " amination modified Fe has been delivered on 2012 41 (12)3O4@SiO2 The preparation of composite magnetic and the absorption research to uranium (VI) ", Fe 3 O 4 magnetic is prepared using chemical coprecipitation Nano-particle, carries out surface modification with tetraethyl orthosilicate (TEOS) and 3- aminopropyl triethoxysilanes (APTES) successively, prepares The modified Fe of surface amination3O4/SiO2Compound particle.Due to being introduced directly into amino with Silicane Method, it grafts on particle The amino amount on surface is very little（Nitrogen content is usually less than 0.05wt%）And presence is isolated each other, cause adsorption capacity low；Meanwhile, Subject matter in terms of material is too small nano particle diameter, and strong adsorption effect easily occurs with other solids, causes magnetic Response is bad, it is difficult to separated from heterogeneous system.
Gong Hongxia etc. was at 2011 69（22）《Chemical journal》On delivered " Cu (II), four ethene five when Cr (VI) coexists Amino-functionalization nanometer Fe304The adsorption mechanism of magnetic polymer material is explored " paper, using by methyl methacrylate and first The copolyreaction generation surface of base glycidyl acrylate carries the magnetic nanoparticle material of epoxy radicals, epoxy radicals occurs again The ring-opening reaction of group prepares TEPA functionalized nano Fe3O4Magnetic polymer material.The distinguishing feature of the method is There is open loop ammonolysis reaction generation product using the amino in TEPA molecule and epoxy radicals, but retain simultaneously（1） Material particle size 30nm, nano-scale particle feature,（2）Nano-sized magnetic particles periphery does not carry out inorganic matter such as silica bag Cover,（3）Coated with Organic Matter layer and inorganic matter kernel between by oleic acid physical absorption connection and non-covalent bond connect,（4）Polymerization Four faults of construction such as ester bond in monomer methacrylic acid ethylene oxidic ester.Due to defect（1）Presence, it is difficult to by the material It is applied to solid-liquid suspension（Mixing）System, defect（2）Cause ferroso-ferric oxide oxidative resistance and acid resistance not strong, defect（3）Lead Organic coating layer or amino is caused easily to come off, defect（4）Cause ester bond that hydrolysis easily occurs under acid and alkalescence condition With addition substitution reaction, the range of application of such material is limited.
Therefore, for water body, soil and solid-liquid suspension（Mixing）Heavy metal pollution is removed in system（Purification）Material and Method also needs to carry out new innovation and creation.
Magnetic retention polyamino adsorbent particulate material prepared by the present invention contains the nothings different from above-mentioned multinomial invention The organic many shell core-shell structures of machine and polyamino adsorption group, utilizePolyamino group has to valuable metal and heavy metal ion Selective suction-operated,This magnetic-particle material has easily by magnet or concentration equipment from water body, soil, solid-liquid suspension Separated in system, renewable, the advantage of low cost, be easy to carry out the large, medium and small many scale heavy metal pollutions removings of multiple types only It is turned into industry, overall process is without a large amount of dirts（It is useless）Water is produced, and does not cause secondary pollution or strange land to pollute, and can reclaim heavy metal.
The content of the invention
The technical problems to be solved by the invention are directed to the deficiency that above-mentioned prior art is present, there is provided a kind of grain diameter Moderate, Stability Analysis of Structures, amino content be big or adsorption capacity big, be resistant to calcium ions and magnesium ions interference, can be in solid-liquid heterogeneous system and width pH The magnetic retention polyamino adsorbent particulate material of many amine groups of Surface coating used in the range of value.
A kind of magnetic retention polyamino adsorbent particulate material (many ammonia of abbreviation magnetic of many amido adsorption groups of Surface coating Base particle), it is characterised in that its structure is the internal many shell core-shell structures of organic-inorganic and peripheral polyamino group composition, Polyamino group uses carbonnitrogen bond as between its peripheral adsorption group, with many shell core-shell structures of organic-inorganic（C—N）Connection.
Above-mentioned magnetic polyamino particle, it is characterized by many shell core-shell structures of organic-inorganic are by magnetic powder particle kernel Or its aggregate, inorganic matter clad, Coated with Organic Matter layer composition.Its magnetic powder particle kernel or its aggregate and inorganic matter Clad, is connected between inorganic matter clad and Coated with Organic Matter layer with covalent bond.
Above-mentioned magnetic polyamino particle, it is characterized by polyamino group is used as its peripheral adsorption group, it is organic with inorganic By carbonnitrogen bond between many shell core-shell structures（C—N）Connection.
Above-mentioned magnetic polyamino particle, it is characterized by carbonnitrogen bond（C—N）The carbonnitrogen bond in amide groups, or secondary amine or Carbonnitrogen bond in tertiary amine.
Above-mentioned magnetic polyamino particle, its particle size range is 0.02 --- 1000 μm, preferably 0.5-500.0 μm.
Above-mentioned magnetic polyamino particle, in its inorganic organic many shell core-shell structure：Described magnetic powder kernel choosing From magnetite pulverulent body or Fe3O4One or more mixtures in powder, iron powder or other artificial synthesized magnetic powder materials, Particle size range is 0.01-100.0 μm；Described inorganic matter clad is usually silica, or the oxidation of titanium, aluminium etc. Thing.The thickness of clad is 0.001-10.0 μm, and coated particle particle size range is 0.021 --- 500 μm, preferably 0.4-200.0 μm.Described Coated with Organic Matter layer is polymethyl methacrylate or its copolymer.The thickness of Coated with Organic Matter layer is 0.010- 200.0μm。
Above-mentioned magnetic polyamino particle, it is characterized by magnetic retention polyamino adsorbent particulate material nitrogen content is more than 0.01wt%, preferably greater than 1.20wt%.
To make this product, the technical solution adopted in the present invention is：
Prepare inorganic matter clad：Use magnetic powder kernel（Selected from magnetite pulverulent body or Fe3O4Powder, iron powder or other people One or more mixtures in the magnetic powder material of work synthesis, particle size range is 0.02-100.0 μm）With tetraethyl orthosilicate Deng reaction, the magnetic powder material of inorganic matter cladding is prepared, its structure can use Fe3O4@ SO2Or FS is represented.
Surface double-bond：Reacted with FS and carbon-carbon double bond silane coupler, prepare FS magnetic-particle coated with carbon carbon The magnetic powder material of double bond.Its typical preparation process is described as follows：It is core shell structure matrix with FS, adds organic solvent second Alcohol, after stirring forms unit for uniform suspension, adds VTES etc. and catalyst is stirred, and makes it in matrix There is Silanization reaction in surface, then isolate granular materials with magnet, obtain the magnetic powder material of Surface coating carbon-carbon double bond Material FS@- double bond.
Prepare Coated with Organic Matter layer：Under initiator effect, occur with FS@- double bond and carbon-carbon double bond polymerized monomer solid Body surface face graft copolymerization, generates the Surface coating magnetic powder material FS@- organo-functional group of organo-functional group.
Prepare magnetic polyamino particle：In at 10-80 DEG C, mixed with multiamino compound with FS@- organo-functional group, Generation generates carbonnitrogen bond（C—N）Ammonolysis reaction after obtain product.
Using this product, with reference to magnetic separation technique, can solve contaminated by heavy metals water body, farmland and place soil, The systems such as fowl and animal excrement, sludge, riverbed sludge（Liquid, solid-liquid suspension system）Purifying problem.Including heavy metal pollution The system such as water body, farmland and place soil, fowl and animal excrement, sludge, riverbed sludge（Liquid, solid-liquid suspension system）In it is specific heavy Metal carries out adsorbing and trapping, then carries out magnetic separation and is separated with system.It is as follows in detail：
A kind of utilization magnetic retention polyamino adsorbent particulate material removes the method for heavy metal pollution of soil, including in soil Specific heavy metal carry out adsorbing and trapping, then carry out magnetic separation and separated with soil material.The present invention to specific heavy metal substance such as The effects with directive property such as lead cadmium chromium mercury arsenical copper nickel zinc, magnetic retention adsorbent with recycling utilization, and be able to can be reclaimed Heavy metal.Application method is included but is not limited to：1. mud processed, 2. catches magnetic retention polyamino adsorbent with mud mixing and absorption Collection heavy metal；3. the magnetic retention polyamino adsorbent that heavy metal will have been adsorbed with magnet is separated with mud；4. by magnetic retention Polyamino sorbent material is reclaimed together with heavy metal, and concentration carries out disposal of resources.
A kind of utilization magnetic retention polyamino adsorbent particulate material removes the method for heavy metal pollution in feces of livestock and poultry, bag Specific heavy metal in including to feces of livestock and poultry carries out adsorbing and trapping, then carries out magnetic separation and is separated with feces of livestock and poultry.The present invention is to spy Determine the heavy metal substance such as effect with directive property such as lead cadmium chromium mercury arsenical copper nickel zinc, magnetic retention adsorbent can be with regeneration cycle profit With, and heavy metal can be reclaimed.Application method is included but is not limited to：1. magnetic retention polyamino adsorbent and feces of livestock and poultry are starched Liquid mixing and absorption trap heavy metals；2. the magnetic retention polyamino adsorbent and feces of livestock and poultry that heavy metal will have been adsorbed with magnet are starched Liquid is separated；3. magnetic retention polyamino sorbent material is reclaimed together with heavy metal, concentration carries out disposal of resources.
A kind of utilization magnetic retention polyamino adsorbent particulate material removes the method for Heavy Metal Pollution in Sludge, including right Specific heavy metal in sludge carries out adsorbing and trapping, then carries out magnetic separation and is separated with Coal Chemical Industry sludge.The present invention is to a specific huge sum of money Category the material such as effect with directive property such as lead cadmium chromium mercury arsenical copper nickel zinc, magnetic retention adsorbent can with recycling utilization, and Heavy metal can be reclaimed.Application method is included but is not limited to：1. magnetic retention polyamino adsorbent is mixed into suction with sludge slurries Attached trap heavy metals；2. the magnetic retention polyamino adsorbent and Coal Chemical Industry sludge slurries point of heavy metal will have been adsorbed with magnet From；3. magnetic retention polyamino sorbent material is reclaimed together with heavy metal, concentration carries out disposal of resources.
A kind of utilization magnetic retention polyamino adsorbent particulate material removes the method for heavy metal pollution in riverbed sludge, bag Specific heavy metal in including to riverbed sludge carries out adsorbing and trapping, then carries out magnetic separation and is separated with riverbed sludge.The present invention is to spy Determine the heavy metal substance such as effect with directive property such as lead cadmium chromium mercury arsenical copper nickel zinc, magnetic retention adsorbent can be with regeneration cycle profit With, and heavy metal can be reclaimed.Application method is included but is not limited to：1. riverbed sludge is suctioned out to form mud, 2. consolidates magnetic Body polyamino adsorbent and riverbed sludge slurries mixing and absorption trap heavy metals；3. the magnetic that heavy metal will have been adsorbed with magnet is consolidated Body polyamino adsorbent is separated with riverbed sludge slurries；4. magnetic retention polyamino sorbent material is returned together with heavy metal Receive, concentration carries out disposal of resources.
The present invention is to such as effect with directive property, magnetic such as lead cadmium chromium mercury arsenical copper nickel zinc uranium thorium and europium of specific heavy metal substance Property solid absorbent with recycling utilization, and can reclaim heavy metal.Application method is included but is not limited to：1. magnetic is consolidated Body polyamino adsorbent and aqueous solution mixing and absorption trap heavy metals；2. many ammonia of magnetic retention that heavy metal will have been adsorbed with magnet Base adsorbent is separated with water body；3. magnetic retention polyamino sorbent material is reclaimed together with heavy metal, concentration carries out resource Change disposal.The present invention can make up existing heavy metal pollution of soil, chemical method, Physical, bioanalysis and repair the deficiency of presence, to some Metal ion has the effect of directive property, and simple with method, magnetic carrier particles material can be with recycling utilization, treatment cost It is low, the advantage of technique of preparing and benficiation machinery can be played, large, medium and small various scale pollutant heavy-metal movements can be carried out except decrement Purification is repaired, and overall process is without a large amount of dirts（It is useless）Water is produced, and does not cause secondary pollution or strange land to pollute, and can reclaim a huge sum of money Category.
The present invention is described below：
1st, according to such scheme, stepMiddle magnetic powder generally refers to soft magnetic materials.Soft magnetic materials（soft magnetic material）Magnetic material with low-coercivity and high magnetic permeability.Soft magnetic materials is easy to magnetization, is also easy to demagnetization.Soft magnetism material Material species is a lot, and the present invention is can be used in principle.It is applicable but is not limited to soft magnetism powder body material of the invention and generally refers to magnetic Iron ore powder, Fe3O4One or more mixtures in powder, iron powder etc., particle size range is 0.02-100.0 μm.
2nd, according to such scheme, stepMiddle carbon-carbon double bond silane coupler is one kind of silane coupler, and its classics is produced Thing can use formula YSiX3Represent.When carbon-carbon double bond is contained in Y group, referred to as carbon-carbon double bond silane coupler.It is applicable but does not limit Have in carbon-carbon double bond silane coupler of the invention：The second of vinyl three（First）TMOS, vinyl trichlorosilane, γ-（Methyl Acryloyl-oxy）Propyl trimethoxy silicane.
3rd, according to such scheme, stepMiddle carbon-carbon double bond polymerized monomer generally refers to methyl acrylic ester and propylene Acid esters compound.Being applicable but being not limited to methacrylate of the invention includes：Methyl methacrylate, methacrylic acid second Ester, GMA, being applicable but being not limited to acrylate of the invention includes：Methyl acrylate, acrylic acid second Ester etc..
4th, according to such scheme, stepMiddle multiamino compound is referred in molecule comprising more than two amino（Including Brothers tertiary amino）Organic compound.Being applicable but being not limited to multiamino compound of the invention has：Polyethyleneimine,It is poly- Allylamine (hydrochloride)：Molecular formula (C3H7N)n .XHCl, it is adaptable to polymerization degree n=30 of the invention；Oligomeric ethyleneamine：It is applicable Have in of the invention：Ethylenediamine, diethylenetriamine, triethylene tetramine, TEPA；The degraded of natural products shitosan Thing：Shitosan (chitosan) chemical name is Chitosan (1-4) -2- amino-betas-D-Glucose, with hydrochloric acid effect, hair Raw glycosidic bond fracture, forms the degradation product that many degree of polymerization are not waited.
5th, according to such scheme, its preparation method is characterised by between organic coating layer and inorganic coating layer by graft copolymerization Reaction generation carbon-carbon single bond this stabilization covalent bond connection, structure is sufficiently stable, it is to avoid inorganic layer in many shells and organic Layer phenomenon peeling-off in use.
6th, according to such scheme, its preparation method is characterised by anti-on multiamino compound and magnetic-particle material shell There is ammonolysis reaction generation carbonnitrogen bond and be grafted on described magnetic-particle material surface in answering property group, structure is sufficiently stable, keeps away Exempt from adsorption group and hold caducous shortcoming in use.
7th, according to such scheme, magnetic polyamino particle size range is 0.5-500.0 μm.Its grain diameter is sized for It is applied to solid-liquid suspension（Mixing）System carries out magnetic separation separation, magnetic particle recovery reaches more than 99%, it is to avoid nano-scale magnetic Particle is easily and solid-liquid suspension（Mixing）There is strong adsorption in the solid granulates in system（Stick）, it is difficult to Magneto separate is carried out, is caused Shortcoming of the rate of recovery less than 70%.
8th, according to such scheme, its adsorption group is characterized as polyamino group, and calcium ions and magnesium ions do not produce interference.
9th, according to such scheme, magnetic polyamino particle nitrogen content is typically larger than 1.20wt%, and larger adsorption capacity is allowed to With actually used value.
10 according to such scheme, and many shell core-shell structures are coated by magnetic powder particle kernel or its aggregate, inorganic matter Layer, Coated with Organic Matter layer composition.
11st, according to such scheme, it is applicable but is not limited to inorganic matter clad of the invention usually silica, it is also possible to It is the oxide of titanium, aluminium etc..The thickness of clad is 0.005-0.05 μm, and coated particle particle size range is 0.2-200.0 μm.
12nd, according to such scheme, Coated with Organic Matter layer is PMAm or methyl methacrylate and methyl-prop Copolymer of acrylamide etc..The thickness of Coated with Organic Matter layer is 0.05-0.80 μm.
13rd, according to such scheme, many shell core-shell structures, it is characterised in that its magnetic kernel and inorganic matter clad, nothing It is connected with covalent bond between machine thing clad and Coated with Organic Matter layer.
14th, according to such scheme, preparation method one：A kind of preparation method characteristic of magnetic polyamino particle is polyamino When compound is polyethyleneimine, polyallylamine base, oligomeric ethyleneamine base, including following typical case's preparation process：
Prepare magnetic powder matrix：Use Fe3O4The reaction such as powder and tetraethyl orthosilicate, prepares inorganic matter such as silica bag The magnetic powder material for covering, its structure can use Fe3O4@ SO2Or FS is represented.
Prepare double bond layer coated magnetic powder body material：Reacted with FS and carbon-carbon double bond silane coupler, prepare double bond layer The magnetic powder material of cladding.Its typical preparation process is described as follows：It is core shell structure matrix with FS, adds organic solvent second Alcohol, after stirring forms unit for uniform suspension, adds VTES etc. and catalyst is stirred, and makes it in matrix There is Silanization reaction in surface, then isolate granular materials with magnet, obtain the magnetic powder material of Surface coating carbon-carbon double bond Material FS@- double bond.
Prepare the coated magnetic powder body materials such as methyl esters layer：With FS@- double bond and carbon-carbon double bond polymerized monomer, such as methyl-prop , under the effect of initiator benzoyl peroxide, there is surface of solids graft copolymerization in e pioic acid methyl ester, generating Surface coating has Magnetic powder material FS@- carboxylate methyl ester of machine thing active function groups such as carboxylate methyl ester etc. etc..
Prepare final product：With FS@- carboxylate methyl ester etc. and multiamino compound, at 10-80 DEG C, there is carboxylate Deng ammonolysis reaction, obtain final product --- magnetic polyamino particle.
Preparation method two：A kind of magnetic polyamino particle, the preparation method characteristic is multiamino compound for shell is poly- During glycosyl, including following preparation process：
Prepare magnetic powder matrix：Use Fe3O4The reaction such as powder and tetraethyl orthosilicate, prepares inorganic matter such as silica bag The magnetic powder material for covering, its structure can use Fe3O4@ SO2Or FS is represented.
Prepare double bond layer coated magnetic powder body material：Reacted with FS and carbon-carbon double bond silane coupler, prepare double bond layer The magnetic powder material of cladding.Its typical preparation process is described as follows：It is core shell structure matrix with FS, adds organic solvent second Alcohol, after stirring forms unit for uniform suspension, adds VTES etc. and catalyst is stirred, and makes it in matrix There is Silanization reaction in surface, then isolate granular materials with magnet, obtain the magnetic powder material of Surface coating carbon-carbon double bond Material FS@- double bond.
Prepare the magnetic powder body materials such as the claddings such as methyl esters layer：With FS@- double bond and carbon-carbon double bond polymerized monomer, such as methyl , under the effect of initiator benzoyl peroxide, there is surface of solids graft copolymerization in methyl acrylate, generate Surface coating Magnetic powder material FS@- carboxylate methyl ester of organic matter active function groups such as carboxylate methyl ester etc. etc..
Prepare degradation of chitosan product：PH value is adjusted to pH=2 ± 0.5,30- by the acetum hydrochloric acid of shitosan Heated 30-120 minutes at 80 DEG C, be cooled to room temperature, pH value is then adjusted to 8-10 with sodium hydroxide solution, obtain the drop of shitosan Solution product.
Prepare final product：Mixed with degradation of chitosan product with FS@- carboxylate methyl ester etc., at 10-80 DEG C, occurred The ammonolysis reaction of carboxylate etc., obtains final product --- and take shitosan as the magnetic polyamino particle of polyamino clad.
Compared with prior art, the beneficial effects of the invention are as follows：
1st, magnetic polyamino particle size range of the present invention is 0.5-500.0 μm, it is to avoid nano particle is easily by other The shortcoming of solid matter strong adsorption, is especially suitable for carrying out Magneto separate operation using magnetic separator, and material magnetic separation recovery rate is more than 99%。
2nd, magnetic polyamino particle of the present invention has inorganic organic many shell core-shell structures, magnetic powder particle kernel With inorganic matter clad, it is connected with covalent bond between inorganic matter clad and Coated with Organic Matter layer, polyamino group and magnetic Property powder is main is connected with amido link, structure is sufficiently stable, can mix in pH scopes selective absorption water body wide, solid-liquid（It is outstanding It is floating）The noble metal such as the heavy metal such as Zn, Pb, Cd, Hg, Cr, As, Cu, Ni and Au, Ag in system, calcium and magnesium plasma does not produce interference Effect.
3rd, magnetic polyamino particle of the present invention, after having adsorbed heavy metal and noble metal, easily utilizes magnetic separation or filtering Method is from water body, soil, solid-liquid suspension（Mixing）Separated in system, it is possible to reclaim heavy metal with the method for acidleach etc., Make material regeneration and reuse, it is adaptable to which the industry such as environmental protection, pollution control, bio-separation, ore dressing, hydrometallurgy is carried out The adsorption and enrichment such as heavy metal and noble metal is separated.
Brief description of the drawings
Fig. 1 is the structural representation of core-shell structure magnetic solid polyamino adsorbent particulate material；
Fig. 2 is the preparation flow of core-shell structure magnetic solid polyamino adsorbent particulate material；
The magnetic retention polyamino adsorbent particulate material TEM figures of Fig. 3 Surface coating polyamino groups；
The magnetic retention polyamino adsorbent particulate material TEM figures of Fig. 4 Surface coating polyamino groups.
Specific embodiment
For a better understanding of the present invention, with reference to the example content that the present invention is furture elucidated, but the present invention is not only It is limited only to the following examples.
Embodiment 1
A kind of magnetic polyamino granular materials, when polyamino adsorption group therein is from the polyallylamine (salt that the degree of polymerization is 30 Hydrochlorate) when, its preparation method is described below：
It is 0.02 μm of Fe by 40g average grain diameters3O4Magnetic powder, 40g tetraethyl orthosilicates, the mixing of 300ml absolute ethyl alcohols, in The mixture of 40ml ammoniacal liquor and 20ml ethanol is added dropwise with the 1h times at 20 DEG C, then 10h is reacted at 70 DEG C, filtering, ethanol is washed, 110 DEG C dry to obtain FS.
Take 40gFS, the second of 20g vinyl three（First）TMOS, 100ml ethanol mixing, 3ml ammoniacal liquor is stirred at 50 DEG C 10h, makes it that Silanization reaction occur in matrix surface, then isolates granular materials with magnet, and ethanol is washed, 60 DEG C of drying, Obtain the Surface coating magnetic powder material FS@- double bond of carbon-carbon double bond.
40gFS@- double bond is taken, 80g methyl methacrylates, 400ml water, 2g benzoyl peroxides react at 90 DEG C 8h, filtering, washing, 110 DEG C of drying generate the Surface coating magnetic powder material FS@- poly- methyl of polymethyl methacrylate Methyl acrylate.
40g FS@- polymethyl methacrylate is taken with 300g containing polyallylamine (hydrochloride) 30g that the degree of polymerization is 30 In 5h is reacted at 80 DEG C, then the ammonolysis reaction that carboxylate etc. occurs isolates granular materials to the aqueous solution with magnet, and ethanol is washed Wash, 60 DEG C of drying obtain final product --- magnetic polyamino particle.
The magnetic polyamino particle that the present embodiment is obtained is in transmission electron microscope（TEM）Pattern under observation, such as Fig. 3 institutes Show, the light grey shell of one layer of Dark grey core outer cladding, is core shell structure；Nitrogen point is carried out to it using elemental microanalysis method Analysis, its N content is 0.25-0.60wt%, and magnetometric analysis is carried out to it, and its saturation magnetization is 25.00-38.00 emu/g, And soft magnetic materials feature is shown, it is adapted to be used as Magneto separate material.
To 100mL, the adsorption capacity of heavy metal Hg, Cd, Pb etc. is respectively 30.0- to above-mentioned product in the 100mg/L aqueous solution 60.0mg/g；Heavy metal removing rate reaches more than 95%, and the Magneto separate rate of recovery is more than 99.8%；With the salt of the mol/L of 100 mL 0.1 The magnetic retention powder body material 1 h desorption rates of immersion that acid has loaded heavy metal to 1.0 g reach more than 95%, and the material can be again It is raw, recycle.
Embodiment 2
A kind of magnetic polyamino granular materials, when polyamino adsorption group therein comes from diethylenetriamine, its preparation method It is described below：
It is 0.20 μm of ferroso-ferric oxide powder by 40g average grain diameters（Content is more than 99%）, 10g tetraethyl orthosilicates, 300ml without Water-ethanol mixes, and in the mixture of 40ml ammoniacal liquor and 20ml ethanol is added dropwise with the 1h times at 20 DEG C, then reacts 10h at 70 DEG C, Filtering, ethanol washing, 110 DEG C dry to obtain FS.
Take 40gFS, 20g vinyl trichlorosilanes, 200ml ethanol mixing, 3ml ammoniacal liquor stirs 8h at 55 DEG C, make its There is Silanization reaction in matrix surface, then isolate granular materials with magnet, and ethanol washing, 60 DEG C of drying obtain Surface coating The magnetic powder material FS@- double bond of carbon-carbon double bond.
40gFS@- double bond, 60g methyl methacrylates and 20g GMA mixtures are taken, 400ml water, 2g benzoyl peroxides react 12h at 70 DEG C, filtering, washing, 110 DEG C of drying, generate FS@- metering system Sour methyl esters and glycidyl methacrylate copolymer.
Take 40g FS@- methyl methacrylate and contain divinyl with 300g with glycidyl methacrylate copolymer There is carboxylic acid ester groups, the ammonolysis reaction of epoxy radicals or part ammonolysis reaction in 4h is reacted at 80 DEG C in the ethanol solution of triamine 30g, Then granular materials is isolated with magnet, ethanol washing, 60 DEG C of drying obtain final product --- magnetic polyamino particle.
The magnetic polyamino particle that the present embodiment is obtained is in transmission electron microscope（TEM）Pattern under observation, such as Fig. 4 institutes Show, the light grey shell of one layer of Dark grey core outer cladding, is core shell structure；Nitrogen point is carried out to it using elemental microanalysis method Analysis, its N content is 1.20-1.40wt%, and magnetometric analysis is carried out to it, and its saturation magnetization is 25.00-38.00 emu/g, And soft magnetic materials feature is shown, it is adapted to be used as Magneto separate material.
1000 grams of cadmium lead bronze combined contamination soils are taken, 2000 grams of Natural Water mashing are added, 10 grams of above-mentioned products are added, Have a rest stirring 24 hours, with magnet by mud with separate；Heavy metal removing rate reaches 70%, and the Magneto separate rate of recovery is more than 99.8%；With The magnetic retention powder body material immersion 1h desorption rates that the hydrochloric acid of the mol/L of 100 mL 0.1 has loaded heavy metal to 1.0 g reach More than 95%, the material is renewable, recycles.
Embodiment 3
A kind of magnetic polyamino granular materials, when degradation product of the polyamino adsorption group from shitosan therein, its preparation side Method is described below：
It is 50.0 μm of magnetite pulverulent bodies by 40g average grain diameters（Content is more than 90%）, 10g tetraethyl orthosilicates, the anhydrous second of 300ml Alcohol mixes, and in the mixture of 40ml ammoniacal liquor and 20ml ethanol is added dropwise with the 1h times at 20 DEG C, then reacts 10h at 70 DEG C, filtering, Ethanol is washed, and 110 DEG C dry to obtain FS.
Take 40gFS, 20g γ-（Methacryloxypropyl）Propyl trimethoxy silicane, the mixing of 200ml toluene, 3ml ammoniacal liquor, 8h is stirred at 55 DEG C, makes it that Silanization reaction occur in matrix surface, then isolate granular materials with magnet, ethanol is washed, 60 DEG C of drying, obtain the magnetic powder material FS@- double bond of Surface coating carbon-carbon double bond.
Take 40gFS@- double bond, 60g GMAs and 10g ethyl acrylate mixtures, 400ml water, 2g potassium peroxydisulfates, react 12h at 70 DEG C, filtering, washing, 110 DEG C of drying, generate FS@- GMA With ethyl acrylate copolymer.
40g FS@- GMA is taken with ethyl acrylate copolymer and the drop of 300g chitosan-containings There is ammonolysis reaction or part ammonolysis reaction in the solution of solution thing 30g, then isolate granular material with magnet in 4h is reacted at 80 DEG C Material, ethanol washing, 60 DEG C of drying obtain final product --- magnetic polyamino particle.
The magnetic polyamino particle that the present embodiment is obtained is in transmission electron microscope（TEM）Pattern under observation, there is similar Pattern shown in Fig. 4, the light grey shell of one layer of Dark grey core outer cladding, is core shell structure；Using elemental microanalysis method to it Nitrogen analysis is carried out, its N content is 0.30-0.40wt%, and magnetometric analysis is carried out to it, its saturation magnetization is 15.00- 18.00 emu/g, and soft magnetic materials feature is shown, it is adapted to be used as Magneto separate material.
Take 1000 grams of zinc-copper combined pollution fowl and animal excrement slurries（Solid content 30wt%）, 10 grams of above-mentioned products are added, interval Stirring 24 hours, with magnet by mud with separate；Heavy metal removing rate reaches 95%, and the Magneto separate rate of recovery is more than 99.8%；With 100 The hydrochloric acid of the mol/L of mL 0.1 1.0 g have been loaded heavy metal magnetic retention powder body material immersion 1h desorption rates reach 95% with On, the material is renewable, recycles.
Embodiment 4
A kind of magnetic polyamino granular materials, when polyamino adsorption group therein comes from polyethyleneimine, its preparation method It is described below：
It is 50.0 μm of iron powders by 40g average grain diameters（Content is more than 98%）, 10g tetraethyl orthosilicates, 300ml absolute ethyl alcohols mix Close, in the mixture of 40ml ammoniacal liquor and 20ml ethanol is added dropwise with the 1h times at 20 DEG C, then react 10h at 70 DEG C, filtering, ethanol Washing, 110 DEG C dry to obtain FS.
Take 40gFS, 20g γ-（Methacryloxypropyl）Propyl trimethoxy silicane, the mixing of 200ml toluene, 3ml ammoniacal liquor, 8h is stirred at 55 DEG C, makes it that Silanization reaction occur in matrix surface, then isolate granular materials with magnet, ethanol is washed, 60 DEG C of drying, obtain the magnetic powder material FS@- double bond of Surface coating carbon-carbon double bond.
Take 40gFS@- double bond, 30g methyl methacrylates and 20g ethyl acrylate mixtures, 400ml water, 2g over cures Sour potassium, reacts 12h at 70 DEG C, filtering, washing, 110 DEG C of drying, generates FS@- methyl methacrylate and ethyl acrylate Copolymer.
Take 40g FS@- methyl methacrylate and ethyl acrylate copolymer, 500g water, 10g polyethyleneimines, in Reaction 4h is mixed at 80 DEG C, ammonolysis reaction or part ammonolysis reaction occur, then isolate granular materials, ethanol with magnet Washing, 60 DEG C of drying, obtains final product --- magnetic polyamino particle.
The magnetic polyamino particle that the present embodiment is obtained is in transmission electron microscope（TEM）Pattern under observation, there is similar Pattern shown in Fig. 3, the light grey shell of one layer of Dark grey core outer cladding, is core shell structure；Using elemental microanalysis method to it Nitrogen analysis is carried out, its N content is 0.30-0.40wt%, and magnetometric analysis is carried out to it, its saturation magnetization is 24.00- 28.00 emu/g, and soft magnetic materials feature is shown, it is adapted to be used as Magneto separate material.
Take 1000 grams of municipal sludge slurries of zinc-copper lead combined pollution（Solid content 20wt%）, 10 grams of above-mentioned products are added, Intermittent stirring 24 hours, with magnet by mud with separate；Heavy metal removing rate reaches 75%, and the Magneto separate rate of recovery is more than 99.8%； The magnetic retention powder body material that 1.0 g have been loaded with heavy metal with the hydrochloric acid of the mol/L of 100 mL 0.1 soaks 1h desorption rates and reaches To more than 95%, the material is renewable, recycles.
Embodiment 5
A kind of magnetic polyamino granular materials, when polyamino adsorption group therein comes from diethylenetriamine, its preparation method It is described below：
It is 0.20 μm of ferroso-ferric oxide powder by 40g average grain diameters（Content is more than 99%）, 10g tetraethyl orthosilicates, 300ml without Water-ethanol mixes, and in the mixture of 40ml ammoniacal liquor and 20ml ethanol is added dropwise with the 1h times at 20 DEG C, then reacts 10h at 70 DEG C, Filtering, ethanol washing, 110 DEG C dry to obtain FS.
Take 40gFS, 20g vinyl trichlorosilanes, 200ml ethanol mixing, 3ml ammoniacal liquor stirs 8h at 55 DEG C, make its There is Silanization reaction in matrix surface, then isolate granular materials with magnet, and ethanol washing, 60 DEG C of drying obtain Surface coating The magnetic powder material FS@- double bond of carbon-carbon double bond.
40gFS@- double bond, 60g methyl methacrylates and 20g GMA mixtures are taken, 400ml water, 2g benzoyl peroxides react 12h at 70 DEG C, filtering, washing, 110 DEG C of drying, generate FS@- metering system Sour methyl esters and glycidyl methacrylate copolymer.
Take 40g FS@- methyl methacrylate and contain divinyl with 300g with glycidyl methacrylate copolymer There is carboxylic acid ester groups, the ammonolysis reaction of epoxy radicals or part ammonolysis reaction in 4h is reacted at 80 DEG C in the ethanol solution of triamine 30g, Then granular materials is isolated with magnet, ethanol washing, 60 DEG C of drying obtain final product --- magnetic polyamino particle.
The magnetic polyamino particle that the present embodiment is obtained is in transmission electron microscope（TEM）Pattern under observation, there is similar Pattern shown in Fig. 3, the light grey shell of one layer of Dark grey core outer cladding, is core shell structure；Using elemental microanalysis method to it Nitrogen analysis is carried out, its N content is 1.20-1.40wt%, and magnetometric analysis is carried out to it, its saturation magnetization is 25.00- 38.00 emu/g, and soft magnetic materials feature is shown, it is adapted to be used as Magneto separate material.
Take 1000 grams of cadmium lead bronze arsenic combined pollution bed mud in river, add 2000 grams of Natural Waters mashing, add 10 grams it is above-mentioned Product, intermittent stirring 24 hours, with magnet by mud with separate；Heavy metal removing rate reaches 70%, and the Magneto separate rate of recovery is more than 99.8%；The magnetic retention powder body material that 1.0 g have been loaded with heavy metal with the hydrochloric acid of the mol/L of 100 mL 0.1 soaks 1h and takes off Attached rate reaches more than 95%, and the material is renewable, recycles.
The above is only the preferred embodiment of the present invention, it is noted that come for one of ordinary skill in the art Say, without departing from the concept of the premise of the invention, can also make some modifications and variations, these belong to of the invention Protection domain.

Claims (14)

1. a kind of magnetic retention polyamino adsorbent particulate material of many amido adsorption groups of Surface coating, it is characterised in that its knot Structure is made up of the polyamino group of internal inorganic organic many shell core-shell structures and periphery.
2. the magnetic retention polyamino absorbent particles material of many amido adsorption groups of Surface coating according to claim 1 Material, it is characterized by inorganic organic many shell core-shell structures are had by magnetic powder particle kernel or its aggregate, inorganic matter clad Machine thing clad is constituted, its magnetic powder particle kernel or its aggregate and inorganic matter clad, inorganic matter clad with it is organic It is connected with covalent bond between thing clad.
3. magnetic retention polyamino absorbent particles of many amido adsorption groups of Surface coating according to claim 1 and 2 Material, it is characterized by polyamino group as between its peripheral adsorption group, with inorganic organic many shell core-shell structures by carbon nitrogen Key（C—N）Connection.
4. the magnetic retention polyamino absorbent particles material of many amido adsorption groups of Surface coating according to claim 3 Material, it is characterized by carbonnitrogen bond（C—N）It is the carbonnitrogen bond in the carbonnitrogen bond in amide groups, or secondary amine or tertiary amine.
5. magnetic retention polyamino adsorbent particulate material according to claim 1 and 2, its particle size range is 0.02 --- 1000 μm, preferably 0.5-500.0 μm.
6. magnetic retention polyamino adsorbent particulate material according to claim 1 and 2, its inorganic organic many shell core-shell In structure：Described magnetic powder kernel is selected from magnetite pulverulent body or Fe3O4Powder, iron powder or other artificial synthesized magnetic powders One or more mixtures in body material, particle size range is 0.01-100.0 μm；Described inorganic matter clad is usually two Silica, or the oxide of titanium, aluminium etc., the thickness of clad is 0.001-10.0 μm, and coated particle particle size range is 0.021 --- 500 μm, preferably 0.4-200.0 μm, described Coated with Organic Matter layer is polymethyl methacrylate or its copolymerization Thing, the thickness of Coated with Organic Matter layer is 0.010-200.0 μm.
7. magnetic retention polyamino adsorbent particulate material according to claim 1 and 2, it is characterized by many ammonia of magnetic retention Base adsorbent granular materials nitrogen content is more than 0.01wt%, preferably greater than 1.20wt%.
8. a kind of magnetic retention polyamino adsorbent particulate material, the feature of its preparation method is peripheral many amine groups by many ammonia There is aminating reaction acquisition in based compound, comprise the following steps with the reactive functional groups on organic coating layer：
Prepare inorganic matter clad：Use magnetic powder kernel（Selected from magnetite pulverulent body or Fe3O4 powders, iron powder or other are artificial One or more mixtures in the magnetic powder material of synthesis, particle size range is 0.02-100.0 μm）With tetraethyl orthosilicate etc. Reaction, prepares the magnetic powder material of inorganic matter cladding, and its structure can use Fe3O4@ SO2Or FS is represented;Surface double-bond： Reacted with FS and carbon-carbon double bond silane coupler, prepare the magnetic powder material of FS magnetic-particle Surface coating carbon-carbon double bonds;Its Typical preparation process is described as follows：It is core shell structure matrix with FS, adds organic solvent ethanol, stirring forms unit for uniform suspension Afterwards, add VTES etc. and catalyst is stirred, make it that Silanization reaction occur in matrix surface, so Granular materials is isolated with magnet afterwards, the magnetic powder material FS@- double bond of Surface coating carbon-carbon double bond is obtained;Prepare organic Thing clad：Under initiator effect, there is surface of solids graft copolymerization with FS@- double bond and carbon-carbon double bond polymerized monomer, Generate the Surface coating magnetic powder material FS@- organo-functional group of organo-functional group;Prepare the absorption of magnetic retention polyamino Agent granular materials：In at 10-80 DEG C, mixed with multiamino compound with FS@- organo-functional group, generation carbonnitrogen bond occurs（C— N）Ammonolysis reaction after obtain product.
9. the magnetic retention polyamino adsorbent particulate material according to right 8, the feature of its preparation method is peripheral polyamines There is aminating reaction and obtain in base group, including following step by the reactive functional groups on multiamino compound and organic coating layer Suddenly：
Prepare Coated with Organic Matter layer：With FS@- double bond and carbon-carbon double bond polymerized monomer, under initiator effect, there is solid table Face graft copolymerization, generates the Surface coating magnetic powder material FS@- organo-functional group of organo-functional group, such as in over cure Under sour potassium effect, FS@- double bond is copolymerized conjunction reaction, generation FS@- polymethyl methacrylate etc. with methyl methacrylate;Prepare magnetic retention polyamino adsorbent particulate material：In at 10-80 DEG C, with FS@- organo-functional group and multiamino compound , there is generation carbonnitrogen bond in mixing（C—N）Ammonolysis reaction after obtain product;FS@- polymethyl methacrylate etc. and ethylenediamine Mixing, generates the ammonolysis reaction of N substituted amide key, obtains final product --- the magnetic of many amido adsorption groups of Surface coating Solid polyamino adsorbent particulate material.
10. a kind of utilization magnetic retention polyamino adsorbent particulate material removes the method for Heavy Metals in Waters pollution, including right Specific heavy metal in the aqueous solution carries out adsorbing and trapping, then carries out magnetic separation and is separated with water body, and the present invention is to specific heavy metal thing The matter such as effect with directive property such as lead cadmium chromium mercury arsenical copper nickel zinc uranium thorium and europium, magnetic retention adsorbent can be with regeneration cycle profit With, and heavy metal can be reclaimed, application method is included but is not limited to：1. magnetic retention polyamino adsorbent is mixed with the aqueous solution Adsorbing and trapping heavy metal；2. the magnetic retention polyamino adsorbent that heavy metal will have been adsorbed with magnet is separated with water body；3. by magnetic Property solid polyamino sorbent material reclaimed together with heavy metal, concentration carry out disposal of resources.
A kind of 11. utilization magnetic retention polyamino adsorbent particulate materials remove the method for heavy metal pollution of soil, including to soil Specific heavy metal in earth carries out adsorbing and trapping, then carries out magnetic separation and is separated with soil material, and the present invention is to specific heavy metal thing The matter such as effect with directive property such as lead cadmium chromium mercury arsenical copper nickel zinc, magnetic retention adsorbent can be with recycling utilization, and can Heavy metal is reclaimed, application method is included but is not limited to：1. mud processed, 2. mixes suction with mud by magnetic retention polyamino adsorbent Attached trap heavy metals；3. the magnetic retention polyamino adsorbent that heavy metal will have been adsorbed with magnet is separated with mud；4. by magnetic Solid polyamino sorbent material is reclaimed together with heavy metal, and concentration carries out disposal of resources.
A kind of 12. utilization magnetic retention polyamino adsorbent particulate materials remove the method for heavy metal pollution in feces of livestock and poultry, bag Specific heavy metal in including to feces of livestock and poultry carries out adsorbing and trapping, then carries out magnetic separation and is separated with feces of livestock and poultry, and the present invention is to spy Determine the heavy metal substance such as effect with directive property such as lead cadmium chromium mercury arsenical copper nickel zinc, magnetic retention adsorbent can be with regeneration cycle profit With, and heavy metal can be reclaimed, application method is included but is not limited to：1. magnetic retention polyamino adsorbent and feces of livestock and poultry are starched Liquid mixing and absorption trap heavy metals；2. the magnetic retention polyamino adsorbent and feces of livestock and poultry that heavy metal will have been adsorbed with magnet are starched Liquid is separated；3. magnetic retention polyamino sorbent material is reclaimed together with heavy metal, concentration carries out disposal of resources.
A kind of 13. utilization magnetic retention polyamino adsorbent particulate materials remove the method for Heavy Metal Pollution in Sludge, including right Specific heavy metal in sludge carries out adsorbing and trapping, then carries out magnetic separation and is separated with Coal Chemical Industry sludge, and invention is to specific heavy metal The material such as effect with directive property such as lead cadmium chromium mercury arsenical copper nickel zinc, magnetic retention adsorbent can be with recycling utilization, and energy Heavy metal is enough reclaimed, application method is included but is not limited to：1. by magnetic retention polyamino adsorbent and sludge slurries mixing and absorption Trap heavy metals；2. the magnetic retention polyamino adsorbent that heavy metal will have been adsorbed with magnet is separated with Coal Chemical Industry sludge slurries； 3. magnetic retention polyamino sorbent material is reclaimed together with heavy metal, concentration carries out disposal of resources.
A kind of 14. utilization magnetic retention polyamino adsorbent particulate materials remove the method for heavy metal pollution in riverbed sludge, bag Specific heavy metal in including to riverbed sludge carries out adsorbing and trapping, then carries out magnetic separation and is separated with riverbed sludge, and the present invention is to spy Determine the heavy metal substance such as effect with directive property such as lead cadmium chromium mercury arsenical copper nickel zinc, magnetic retention adsorbent can be with regeneration cycle profit With, and heavy metal can be reclaimed, application method is included but is not limited to：1. riverbed sludge is suctioned out to form mud, 2. consolidates magnetic Body polyamino adsorbent and riverbed sludge slurries mixing and absorption trap heavy metals；3. the magnetic that heavy metal will have been adsorbed with magnet is consolidated Body polyamino adsorbent is separated with riverbed sludge slurries；4. magnetic retention polyamino sorbent material is returned together with heavy metal Receive, concentration carries out disposal of resources.
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